Lubricant



Patented Apr. 18, 1939 1 UNITED STATES PATENT OFFICE LUBRICANT Carl F. Prutton, Cleveland Heights, Ohio, assign- .or, by mesne assignments, to The Lubri-Zol Development Corporation, Cleveland, Ohio, a corporation Delaware No lh'awing. Application August 17, 1937,

Serial No. 159,801

17 Claims. (0]. 87-9) Thisinvention relates, as indicated, to improved types previously enumerated and over a wide lubricating compositions and more specifically to range of operating conditions such as temperaa new and improved addition agent for lubriture and pressure. eating compositions generally; the method of pro- It is a principal object of my invention to pro- 5 ducing such addition agent and the new and imvide an addition agent for lubricating composi- 5 proved lubricating compositions resulting from tions which is of a chemically complex nature and the use of such addition agent. which has, however, been so stabilized that its This application is a continuation in part of use is now possible under certain types of conmy co-pending applications Ser. No. 111,111, filed ditions under which similar complex materials 1 November 16, 1936, now Patent No. 2,119,556 isof the prior art were entirely unsuited, princisued June 7, 1938, and Ser. No. 737,070, filed July pally on account of their instability.

26, 1934. It is a, further object of my invention to pro- In recent years there has been an increasing vide a method of producing the complex addition demand for improved lubricating compositions agent previously defined, which method is charhaving improved characteristics which are not acterized by its simplicity and low cost of opera- 15 possessed by the usual plain mineral lubricating tion, so that the resultant addition agent is made oils. Among the improved properties thus deavailable at relatively low cost. I sired are extreme pressure characteristics, im- It is a. further object of my invention to proproved cold test, freedom from sludge, etc. vide an improved lubricating composition having 99. In general, it has been found that various types as its principal constituent my improved haloof halogenated organic compounds, when used genated complex addition agent.

as addition agents to mineral lubricating oils, other objects of my invention will appear as produce the above-named improvements to a the description proceeds. ,more pronounced degree than any other class of To the accomplishment of the foregoing and materials, particularly when properly selected related ends, said invention, then, consists of the 25 and used in proper proportions.- means hereinafter fully described, and particu- I The helegeneted O c compounds which larly pointed out in the claims, the following dehave been suggested for use as additions to lubriscription setting forth in detail one approved eating mp si i ns m y be nerally divided combination of ingredients embodying my invenintO tWO Principal C sses, p u s which tion, such disclosed means constituting, however, 30 have been y carefully mi ally isolated, but one of various forms in which the principle treated and stabilized, so that they are suitable of the invention may be used. for use under substantially all conditions and will This invention may be broadly stated as comnot hydrolize and cause destructive corrosion prising the discovery that a new and improved even when Subjected to h temperatures in the stabilized halogenated complex organic addition 35 Presence of Substantial u ts of oisture- 1 agent for lubricating compositions may be satis- The s nd lass f halo nated organic coml'actorily and economically produced and that P ds which have been employed are the halO- lubricating compositions containing the same. genated complex petroleum derivatives whose hav unexpected desirable properties.

P falling within the last-named class, while tion agent may be briefly described as follows:- admirably suited to p v d extreme pressure Any complex or heterogeneous mixture of orluhlieants gears the like ever, ganic compounds such as are found in mineral unsuited for use in lubricants to be employed in oil, mineral oil fractions such as scale wax, parthe crankcases of internal combustion engines afln a t al tar and wood distillates, is 5 due to the fact that heretofore such materials halogenated by the usual procedure well known have contai ed O jectionable amounts of relato those familiar with the art until the composiiv y unstable constituentstion contains from about 10% to about 60% of A halogenated addition agent which is rather halogey complex in its chemical structure,-i. e.,.contains T product immediately resulting from the a rather w de V y Of individual mpounds, halogenation step may be subjected to any of the has, however, certain very desirable character-Y well-known methods of removing the excess haloistics when used as an addition agent in that the gen, aswell ascertain of the more unstable of wide variety of compounds present makes posthe halogen compounds, such processes comprissible the securing oi desired results of the various ing air blowing, treatment with an alkali, etc.

principal appeal has been their low cost. Com- Th process of producing my improved addi- 4o that while the composition may be admirably suit-. t

ed as an extreme pressure addition agent to lubricants useful in. gear cases and the like, nevertheless suchcompounds are too unstable to permit their safe use under conditions such as those encountered in crankcases of internal combustion engines. i

The composition containing a heterogeneous mixture of halogenated compounds prepared in the previously described or any other conventional process, is next treated with anhydrous aluminum chloride or equivalent agent accord-- ing to conventional practice in the well-known Friedel-Crafts or similar condensation reaction. It is preferred, however, that the reaction be carried on to the extent that only the more unstable of the halogenated compounds react, either with one another, or with other compounds present in the composition. During the reaction, therefore, preferably only a minor amount of the combined halogen present in the original halogenated material is removed. The less stable halogenated compounds, if aliphatic, may become attached as alkyl side chains to aromatic compounds, or if of other types, condense with, or react with the same or other compounds present. Certain halogenated aliphatic compounds will also be condensed'with or combine with the same or other aliphatic compounds to form relatively stable products. The final product, depending upon the amount of unstable halogenated compounds originally present and the extent to which the reaction has been carried out, will contain certain proportions of the reaction products, halogenated alkyl or aromatic compounds or both, and also certain proportions of the more stable halogenated compounds originally present.

This treatment with an agent such as AlCla will promote. the condensation of halogenated aromatic with halogenated aliphatic compounds,

' and is also more or less effective in causing the The aluminous sludge resulting from the Friedel-Crafts reaction is then removed according to conventional practice, such as by diluting the mixture with a light hydrocarbon solvent to promote settling and then distilling oil. the solvent.

The resultant composition which comprises the new composition of matter according to my invention, will, when the starting material has been a petroleum derivative, contain minor amounts of .more or less halogenated alkylated aromatic 'conipounds and their derivatives and major proportions of relatively stable halogenated aliphatic compounds.

Inasmuch as the addition agent thus prepared is to be used most generally in a mineral lubricating oil or grease, a certain amount of care should be exercised in selecting the starting material so that the resultant composition, after halogenation and after the Friedel-Crafts reaction,- will be soluble in or miscible with mineral oil and have a sufilciently high boiling point or low vapor pressure that it will not be volatilized at the temperatures encountered during its contemplated use. For example, the resultant composition to be used as an addition agent should have a vapor pressure less than atmospheric at a temperature of 140 and preferably at a temperature of 170.

If certain ofthe addition agents thus prepared are found to be of such a heavy consistency as not to be readily dissolved in or miscible with mineral oil, a mutual solvent may be employed for the purpose of facilitating the preparation of the final composition.

The new addition agent prepared in accordance with the process which comprises one of the be added to the mineral oil base in various percentages from about .1% to about 20% depending upon the particular use for which the final composition is designed. For use under conditions I classified as non-mineral oils and which include animal oils, vegetable oils, etc., used either as the lubricating oil base or likewise as an addition agent to a mineral lubricating oil base. My new and improved addition agent, when added to lubricating oil bases of the character previously described, will be found to desirably improve the extreme pressure characteristics of the resultant composition. In certain instances,

the addition agent will also lower the cold testof such composition, and/or generally improve the sludging characteristics of the composition. All of the halogen compounds present in the heterogeneous mixture are more or less effective in affording extreme pressure characteristics. Certain types of halogenated alkylated aromatic compounds in the heterogeneous mixture are particularly. effective to improve the cold test, of the lubricating compositionsince only small percentages of such compounds are usually required in order to markedly improvthis property of a mineral lubricating oil. The presence of a-wide variety of halogenated compounds in the heterogeneous mixture is particularly advantageous in that the improved properties of the lubricating composition containingsuch heterogeneous mixture as an addition agent extend over a wider range of operating condition than that usually secured by the addition of a single compound.

It is. to be understood that other and similar complex organic mixtures, as above described, may be similarly treated with satisfactory results in producing similar addition agents. Likewise catalysts other than aluminum chloride, such as AlBra, FeCla, ZnClz. etc., which are effective in promoting Friedel-Crafts reaction, may be utilized, although the former is preferred.

The amount of catalyst to be used may be from about to about 10% based on the amount of chlorinated material and in the case of aluminum chloride may preferably be from to 2%. The reaction may be carried out at temperatures up to about 100 C., but preferably, in most cases, below 100" 0., say 20 to 50 C.

The reaction generally should require from about /ti to 2 hours and usually for best results only from to 1 hour is required The reaction may be carried on by adding the catalyst directly to the chlorinated material or the chlorinated material plus an additional amount of aromatic compounds; or it may also be carried out in the presence of a solvent which may be inert or which may be the aromatic compound itself as, for example, benzene.

As an example of the reaction carried out in the absence of a solvent:

3 parts of aluminum chloride were added to 400 parts of chlorinated paramn wax containing 36.4% of chlorine and the mixture heated to a temperature of 75 C. for one-half hour. The mixture was then cooled to room temperature, an equal amount of benzene added and the aluminum sludge removed by washing with dilute hydrochloric acid and then with water. The benzene was then removed by vacuum distillation. The final product contained 32.0% of chlorine.

The stability of the material can be deter.- mined by heating in an iron container at a temperature of about 110 C. until there is evidence of decomposition. The original product under these conditions was stable for hr. and the stabilized product for more than 2 hours.

As an example of the reaction carried on in the presence of the solvent, as well as in the presence of added aromatic compounds? 300 parts of chlorinated wax were diluted with 200 parts of benzene and treated with 2 parts of aluminum chloride at about 25 C. About the same improvement in stability resulted from this treatment. In this case part of the material remained emulsified in the wash water and was removed from the final product. Analysis showed that the part removed had a relatively low chlorine content so that the final product had a higher chlorine content than the original.

As will be seen from the data given for the first example above, the amount of chlorine removed by the reaction was less than 10% of the total chlorine in the original material.

In other cases, a marked improvement in stability was obtained by the removal of less than 5% of the total chlorine originally present.

In general, when stabilizing chlorinated complex organic compounds such as are found in mineral oil, mineral oil fractions, coal tar and wood distillates, the amount of condensing catalyst-added or the extent to which the condensation reaction is carried out in order to effect the desired stabilization of the product when the original material contains from about to about 60% of halogen will be such as to remove during the condensation from a fraction of a percent to about of the chlorine content of the material being stabilized.

The following is an example of the improvement in stability eflected by treatment with aluminum chloride:

A chlorinated petroleum wax containing approximately 40% chlorine, which had been prepared and purified in the usual way and placed in an oven was maintained at a temperature of 110 to 115 C. At the end of approximately thirty minutes certain of the constituents of the material began to decompose as evidenced by a noticeable change in color of the composition accompanied by evolution of hydrogen chloride gas. The same material, after being treated with aluminum chloride in accordance with this invention, was subjected to the same test. No decomposition of any of the constituents was noted until after about five and one-half hours.

Throughout the foregoing description the various compounds referred to have been identified as halogenated compounds. Of the various halogens, chlorine is preferred, principally on account of its low cost and the relative ease by which it ,may be handled as compared with certain other halogens.

Other modes of applying the principle of my invention may be employed instead of the one explained, change being made as regards, the materials employed in carrying out the process, provided the ingredient or ingredients stated in any of the following claims or the equivalent of such stated ingredient or ingredients be employed.

I, therefore, particularly pointout and distinctly claim as my invention:-

1. As a new composition of matter, a halogenated complex mixture of organic compounds of the types found in petroleum oils and in which the less stable compounds have been converted by treatment with a condensing agent of the type represented by anhydrous A1013.

2. As a new-composition of matter, a halogenated naturally occurring complex mixture of organic compounds of the typesfound in petroleum oils, coal tar and wood distillates and in which mixture subsequent to halogenation the less stable compounds have been converted by treatment with a condensing-agent of the type represented by anhydrous AlCls.

3. As a new composition of matter a stabilized complex mixture of organic compounds, which mixture includes substantial amounts of halogenated alkvlated cyclic compounds and relatively stable halogenated aliphatic compounds, prepared by halogenating a naturally occurring complex mixture of organic compounds of the types found in petroleum oils and then eliminating the instability of certain of the components by treatment with a condensing agent of the type best represented by anhydrous AlCls.

4. A composition of matter for use as an addition agent to mineral lubricating oils comprising a naturally occurring complex mixture of organic compounds of the types found in petroleum oils and which mixture has been halogenated and then stabilized by treatment with a condensing agent of the type represented by anhydrous AlCl:;.

5. The method of producing an improved addition agent for lubricating compositions which comprises halogenating complex mixtures of organic compounds of the types found in petroleum oils, coal tar and wood distillates, and then treating such halogenated mixtures with a condensing agent of the type represented by anhydrous AlCl:.

6. A lubricating composition comprising a major proportion of mineral lubricating oil and plex mixture of organic compounds which has been stabilized by treatment with a condensing agent of the type represented by anhydrous AlCla.

7.-A lubricating composition comprising a major proportion of mineral oil and a minor proportion of a halogenated naturally occurring complex mixture of petroleum derivatives, which mixturehas been stabilized by treatment with a condenslng agent of the type best represented by anhydrous AlCh. i

8. A method of producing stabilized lubricating compositions which comprises halogenating a complex mixture of organic compounds of the types found in petroleum oils and then effecting a Friedel-Crafts reaction between the halogenated aromatic compounds and the halogenated aliphatic compounds with the aid of AlCl: and then separating from the A101: and any other solids leaving halogenated alkylated aromatic compounds as a major constituent in the resulting composition, which is then added to a mineral lubricating 011 base.

9. As a new composition of matter, a chlorinated complex mixture of organic compounds of the type; found in petroleum oils and in which the less stable compounds have been converted by treatment with a condensing agent of the type represented'by anhydrous A1013.

10. As a new composition of matter, a chicrinated naturally occurring complex mixture of organic compounds of the types found in petroleum oils, coal tar and wood distillates and in which mixture subsequent to chlorination the less stable compounds have been converted by treatment with a condensing agent of the type represented by anhydrous AlClz.

11. As anew composition of matter a stabilized complex mixture of organic compounds, which mixmreincludessubstantial amounts of chlorinated alkylated cyclic compounds and relatively stable chlorinated aliphatic compounds, prepared by chlorinating a naturally occurring complex mixture of organic compounds of the types found in petroleum oils and then eliminating the instability oi certain of the components by treatment with a condensing agent of the type best represented by anhydrous AlCla. I

12. A composition of matter for use as an addition agent to mineral lubricating oils comprising a naturally occurring complex mixture of organic compounds of the types found in petroleum oils and which mixture has been chlorinated and then stabilized by treatment with a condensing agent of the type represented by anhydrous A1013.

13. The method of producing an improved addition agent for lubricating compositions which comprises chlorinated complex mixtures of organic compounds .of the types found in petroleum oils, coal tar and wood distillates, and then treating such chlorinated mixtures with a condensing agent of the type represented by anhydrous AlCla.

14. A lubricating composition comprising a major proportion of mineral lubricating oil and less than based on the amount of such mineral oil of a chlorinated naturally occun'ing complex mixture of organic compounds which has been stabilized by treatment with a condensing agent of the type represented by anhydrous AlClz.

15. A lubricating composition comprising a major proportion of mineral oil and a minor proportion of a chlorinated naturally occurring complex mixture of petroleum derivatives, which mixture has been stabilized by treatment with a condensing agent of the type best represented by anhydrous AlCla.

16. A method of producing stabilized lubricating compositions which comprises chlorinating a complex mixture of organic compoundsof' the types found in petroleum oils and then eifecting a Frledel-Crafts reaction between the chlorinated aromatic compounds and the chlorinated aliphatic compounds with the aid of A101: and then separating from the A101: and any other solids leaving chlorinated alkylated' aromatic compounds as a major constituent in theresulting composition, which is then added to a mineral lubricating oil base.

1'7. A method of producing stabilized lubricating compositions which comprises halogenatlng a complex mixture of organic compounds of the types found in petroleum oils and then effecting a condensing reaction between the halogenated .compounds with the aid of a re-ag'ent such at A10]: and then separating from the re-agent such as AlCls and any other solids leaving halogenated alkylated aromatic compounds as a major constituent in the resulting composition, which is then added to a mineral lubricating oil base.

CARL F. PRUT'ION. 

